US3832329A - Polyesters prepared from hydroxyarylthio anhydrides - Google Patents

Polyesters prepared from hydroxyarylthio anhydrides Download PDF

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US3832329A
US3832329A US00115778A US11577871A US3832329A US 3832329 A US3832329 A US 3832329A US 00115778 A US00115778 A US 00115778A US 11577871 A US11577871 A US 11577871A US 3832329 A US3832329 A US 3832329A
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hydrogen
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E Geering
N Dachs
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Occidental Chemical Corp
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Hooker Chemical Corp
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Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds

Definitions

  • This invention relates to novel hydroxyarylthio compounds and a process for preparing said compounds by the. reaction of mercaptophenols with reactive unsaturated compounds.
  • 'Mrcaptophenol is not only a mercaptan, but it is also a phenol,and,,,therefore, has both a reactive hydroxyl group and a reactive ring.
  • One-might expect the above alternate reactions to take precedent over the addition of themercaptan group to an unsaturated bond.
  • One could not .predictthat-the compounds of this invention would be'produced by thereaction of a mercaptophenol and a reactive olefin.
  • (0) Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
  • A is aryl of six to 18 carbon atoms
  • R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, aralkaryl, aralkyl, carbalkoxy, carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halogen.
  • R is preferably alkyl, aryl, hydroxy, or halogen
  • Y, Y and Y are preferably hydrogen or alkyl.
  • R, Y, Y and Y are preferably of zero to about ten carbon atoms.
  • A is preferably phenyl, and insaid case, d is from zero to four.
  • R, Y, Yl or Y are halo, they may be chlorine, fluorine, bromine or iodine.
  • the unsaturated compounds that may be used as starting materials in the preparation of the compounds of the present invention are of the following formula:
  • compositions include compounds such as benzoquinone, maleic anhydride, itaconic anhydride, malimide and maleic thioanhydride.
  • the starting mercaptophenol compounds of the present invention are of the formula: HS-A(R) OH; where in A, R and d are as hereinbefore described. Said compounds may be prepared by methods known in the prior art or by the procedure described in copending appllcation Ser. No. 597,228, filed Nov. 28, 1966, now abandoned and refiled as Ser. No. 666,915, filed Sept. 11, 1967, now U.S. 3,468,961.
  • Mercaptophenols such as o-mercaptophenol, p-mercaptophenol, 3,5-dimethyl Z-mercaptophenol, 4- phenyl-Z-mercaptophenol, 3-cyano-2-rnercaptophenol and 4-carboxy-3-mercaptophenol, are typical starting compounds.
  • Typical solvents include benzene, toluene, xylene, heptane, hexane, chloroform, carbon tetrachloride, chlorobenzene, dioxane, N,N-dimethylforr nam1de, N-methyl-Z-pyrrolidone, tetrahydrofuran and dimethylsulfoxide.
  • reaction may be conducted at a temperature of about zero to about 200 degrees centigrade, the preferred temperature is from about to about 150 degrees centigrade.
  • Suitable catalysts include salts of strong bases and alcohols or weak acids, amines, quaternary amine bases and alkali or alkaline earth metals or hydroxides. Examples of catalysts are sodium methylate, sodium acetate, potassium carbonate, triethyl amine, piperidine, triethylene diamine, trimethylbenzylammonium hydroxide and sodium or magnesium and sodium hydroxide.
  • hydroxyarylthio succinic anhydrides and thioanhydrides of the present invention can be reacted with glycols or thioglycols to give the novel polyesters of the present invention.
  • Said novel polyesters contain at least ne unit of the formula Y, Y Y A, R and subscripts d and e fore described.
  • polyesters of the present invention are of the formula are as hereinbe- R and subscript d are as hereinbefore described.
  • Typical glycols or thioglycols that may be used as starting compounds in the preparation of the polyesters of the present invention are as follows: diethylene glycol, ethylene glycol, a,w-dihydroxy[poly(ethyleneoxides)], l, 2-propylene glycol, 3,4-pentanediol, 1,10-decanediol, neopentyldiol, 1,4-cyclohexanediol, diethanol sulfide, 1,4-diethanolbenzene, 1,4-xylylenol, 1,4,5,6,7,7-hexachloro-2,3- bis(hydroxymethyl)bicyclo-(2.2.1 )-heptene-5, ethylenedithiol, hexamethylenedithiol, a,w-dimercapto(po1y
  • glycols and dithiols prepared by the oxyalkylation or thioalkylation of the above compounds and compounds such as 4,4'-isopropylidene diphenol, resorcinol, thiobisphenol, 4,4-dihydroxydiphenyl, aniline and methylamine.
  • the glycol or thioglycol is reacted with the hydroxyarylthio succinic anhydride, or the corresponding dialkyl succinate, when a transesterification procedure is used, at atemperature of about 75 to about 250 degrees centigrade,for a period of about 3 to about 50 hours.
  • No catalyst is required when the polyesterification is conducted by reaction of the hydroxyarylthiosuccinic anhydride.
  • useful catalysts are paratoluenesulfonic acid, or weakly acidic or basic catalysts such as calcium acetate or antimony triox ide.
  • Standard polyesterification procedures are applicable.
  • the rate of esterification can be increased by hastening the elimination of the condensation products, ,water or alcohol. Typically this is accomplished by passing an inert gas stream through the reaction mixture or by maintaining the mixture under reduced pressure, Water can also be removed as it forms by conducting the esterifi-' cation in a water-imiscible solvent, such as toluene, whereby the water is distilled off asa component of an azeotropic distillate. The reaction is followed by periodically determining the carboxylic acid concentration or by monitoring the water or alcohol produced during the'course of the reaction.
  • the c'arboxylic reagent need not be a single compound, but can be composed of several carboxylic compounds, of which one, several, or all can be hydroxyarylthio-sub stituted.
  • the second reactant can be a mixture of several glycols or dimercaptans, Typical non-phenolic carboxylic reagents are fumaric acid, maleic anhydride, phthalic anhydride, pyromellitic anhydride, diethyl fumarate, dimethyl terephthalate, dimethyl 1,4,5 ,6,7,7-hexachlorobicyclo-(2.2.1 -5 -heptane-2,3-dicarboxyl ate.
  • glycol or thioglycol can be replaced by trior higher substituted polyols or polythiols to give across-linked 'polymen-Typical polyols are 1,1,1-trimethylolpropane, glycerol, pentaerythritol, and oxyalkylated derivatives derived from sorbitol, sucrose and phenylenediamine.
  • a portion of the carboxylic reagent can be replaced with unsaturated anhydride or ester, such as those mentioned above, for example, maleic anhydride.
  • unsaturated anhydride or ester such as those mentioned above, for example, maleic anhydride.
  • the resulting polyester can be crosslinked via these unsaturated bonds with a vinyl monomer such as styrene.
  • the phenolic polyester compositions of this invention can be converted to epoxy derivatives by reaction with, for example, epichlorohydrin.
  • the phenolic polyester compositions of this invention can be converted to a polyester substituted with aliphatic hydroxyl groups by treatment with an alkylene oxide, (oxyalkylation), such as ethylene oxide or propylene oxide.
  • alkylene oxide such as ethylene oxide or propylene oxide.
  • ester polyols are useful as reagents for preparing polyurethane polymers by reaction with diisocyanates or polyisocyanates.
  • Typical isocyanates are toluene diisocyanates and the phosgenated reaction products of formaldehyde and aniline.
  • hydroxyarylthiosuccinic anhydrides, succinimides and succinicthioanhydrides of the present invention are useful when incorporated chemically into condensation polymers as stabilizers or as providers of hydroxy groups.
  • the hydroxyl groups are used to chemically attach polymer modifiers, such as dyes, antistatic agents, hydrophobic or .hydrophilic groups, and the like.
  • compositionsof the present invention with carbonyl compounds e.g., formaldehyde or aetone, under acid conditions with or without additional phenol present, gives carboxylic substituted bisphenol or novolak materials which may be esterified with long-chain alcohols to give reagents useful for imparting chemically-bound plasticization to polymers, or which may be incorporated into polycarbonates, for example, to serve as cross-linking sites.
  • reaction of the compounds of the present invention with carbonyl compounds under alkaline conditions gives methylol or resole type materials that will cure on heating.
  • EXAMPLE 2 In a manner similar to Example 1, 5 parts of benzoquinone were reacted with 11.6 parts of o-mercaptophenol. About 7.4 parts of product were obtained. The product, having a melting point of 121-122 degrees centigrade, was identified as 5-(2-hydroxyphenylthio)-2-cyclohexen- 1,4-dione.
  • EXAMPLE 3 In a manner similar to Example 1, 2,4-di-t'butyl-6-mer captophenol was reacted with maleic anhydride. The product, having a melting point of 137-139 degrees centigrade, was identified as 1-(2-hydroxy-3,5-di-t-butylphenylthio) succinic anhydride.
  • EXAMPLE 5 To 58.3 parts of diethylene glycol were added 112 parts (0.5 moles) of (Z-hydroxyphenylthio) succinic anhydride. The mixture was warmed to a temperature of 85 degrees centigrade at which temperature the anhydride went into solution. The solution was heated to 180 degrees centigrade for 75 minutes during which period 6 parts of water were distilled oif. The system was put under millimeters of reduced pressure and the heating con- .tinued. for *one hour at 190 degrees-centigrade and for three hours at 170 degrees centigrade. The resulting product was'a golden yellow resin.
  • EXAMPLE 6 A low molecular weight resole was prepared by a phenol, formaldehyde and sodium hydroxide condensation reaction. Equal amounts of said resole and the polyester of Example were stored at 85 to 95 degrees centigrade for three days. The product was a golden yellow hard resin. When the resole is subjected to the same conditions, it becomes a deep red resin.
  • a polyester comprising at least one unit of the formula wherein (a) e is from zero to one and d is from zero to about six;
  • Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano andhalogen;
  • w is selected from the group consisting of O- and (e) A is aryl of six to 18 carbon atoms; and
  • R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cy no, carboxy and halogen.
  • Y, Y and Y are of zero to about 2O carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
  • Z is selected from the group consisting of --O and (e) A is aryl of six to 18 carbon atoms; and
  • R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halo I V with a glycol or thioglycol at a temperature of about 75 degrees centigrade to about 250 degrees centigrade.
  • R is selected from the group consisting of alkyl, aryl, hydroxy and halogen and d is from zero to six.
  • Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
  • A is aryl of six to 18 carbon atoms
  • R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, carboxy and halogen.
  • R is of zero to about 20 carbon atoms and is selected II I from the group consisting of alkyl, aryl, alkaryl,

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  • Health & Medical Sciences (AREA)
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Abstract

NOVEL COMPOUNDS OF THE FORMULA:

(R)D-A(-OH)-S-(CY2)E-C(-Y2)<(-C(-Y)(-Y1)-CO-Z-CO-)

WHEREIN E IS FROM ZERO TO ONE AND D IS FROM ZERO TO ABOUT SIX, PROVIDED THAT WHEN E IS ZERO, Y1 IS HYDROGEN; AND THAT WHEN E IS ONE, Y2 IS HYDROGEN; Y, Y1 AND Y2 ARE OF ZERO TO ABOUT 20 CARBON ATOMS AND ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, ARALKYL, HYDROGEN, CYANO, AND HALOGEN; Z IS SELECTED FROM THE GROUP CONSISTING OF -NH, -0-, -S- AND -CH=CH-; A IS ARYL OF SIX TO 18 CARBON ATOMS; AND R IS OF ZERO TO ABOUT 20 CARBON ATOMS AND IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, ARALKYL, CARBALKOXY, CARBARYOXY, ALKOXY, ARYLOXY, ALKYLTHIO, ARYLTHIO, HYDROXY, MERCAPTO, CYANO, CARBOXY AND HALOGEN. SAID COMPOUNDS HAVE UTILITY AS POLYMER ADDITIVES. NOVEL POLYESTER DERIVATES OF THE HYDROXYARYLTIO SUCCINIC ANHYDRIDE AND THIOANHYDRIDE COMPOUNDS AND A PROCESS FOR PREPARING SAID POLYESTER.

Description

States Patent 7 Claims ABSTRACT OF DISCLOSURE Novel compounds of the formula:
wherein e is from zero to one and d is from zero to about six, provided that when e is zero, Y is hydrogen; and that when e is one, Y is hydrogen; Y, Y and Y are of zero to about carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano, and halogen; Z is selected from the group consisting of NH, -O-, -S and CH =CH-; A is aryl of six to 18 carbon atoms; and R is 'of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, carbalkoxy, carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halogen. Said compounds have utility as polymer ad-" ditives. Novelpolyester derivatives of the hydroxyarylthio succinic anhydride and thioanhydride compounds and a process for preparing said polyesters.
This is a division of application Ser. No. 749,952, filed Aug. 5, 19 68. and now abandoned,
This invention relates to novel hydroxyarylthio compounds and a process for preparing said compounds by the. reaction of mercaptophenols with reactive unsaturated compounds. p
i The addition of mercaptans to olefins is well known. This reactio'nis described by E. Emmet Reid in Oragnic Chemistry of Bivalent Sulfur, Vol. 11, Chemical Publishing Co., New York City, 1960, pp. 29-34. The reactive unsaturated starting compoundsof the present invention enter into reactions with phenol. .Phenyl esters are formed by acetylation of phenol with, for example, citraconic anhydride. Anhydrides such as maleic anhydride react with phenol to give malein-type products such as phenolmalein. As phenols are readily alkylated by olefins, mercaptophenol similarly could also .be expected to become a1kylatedby olefins.
'Mrcaptophenol is not only a mercaptan, but it is also a phenol,and,,therefore, has both a reactive hydroxyl group and a reactive ring. One-might expect the above alternate reactions to take precedent over the addition of themercaptan group to an unsaturated bond. One could not .predictthat-the compounds of this invention would be'produced by thereaction of a mercaptophenol and a reactive olefin.
, 3,832,329 Patented Aug. 27, 1974 "ice In accordance with the present invention, there are provided novel compounds of the formula:
wherein:
(a) e is from zero to one and d is from zero to about six;
(b) provided that:
(1) when e is zero, Y is hydrogen; and (2) when e is one, Y is hydrogen;
(0) Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
(d) Z is selected from the group consisting of NH,
(e) A is aryl of six to 18 carbon atoms; and
(f) R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, aralkaryl, aralkyl, carbalkoxy, carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halogen.
Also, in accordance with the present invention, there is provided a process for the preparation of the hydroxyarylthio succinic anhydride, succinimide, cyclohexenedione, and succinic thioanhydride compounds and novel polyester derivatives of the hydroxyarylthio succinic anhydride and thioanhydride compounds.
The following are typical of those compounds included within the scope of the present invention:
l-ethyl-1-(4-hydroxyphenylthio) succinimide l-cyano-1-(2-hydroxyphenylthio) succinimide 2-(3-hydroxyphenylthio)-5-cyelohexen-1,4-dione 1-phenyl-2-( 2,3-dichloro-4-hydroxyphenylthio succinic thioanhydride 2-hydroxyphenylthio) succinic thioanhydride Z-hydroxyphenylthio succinic anhydride 2hydroxyphenylthiomethylene succinic anhydride 4-hydroxyphenylthiomethylene succinimide 5-chloro-6-(4-hydroxyphenylthio) -2-cyclohexen-1,4-
dione 1-propyl-2- (2-hydroxynaphthylthio) succinic anhydride 1-dodecy1-2- Z-hydroxyphenylthio succinic anhydride 2- (2-hydroxy-4,5,6-trimethylphenylthio 5-cyc1ohexen- 1,4-dione 1-benzyl-2- 3-hydroxyphenylthio succinic thioanhydride 1-tolyl-2-(4-hydroxyphenylthio succinimide 2- 3hydroxyphenylmethylene) succinic thioanhydride In the compounds of the present invention the carbonyl groups are activating groups that promote the addition reaction of a mercaptophenol to an unsaturated carboncarbon bond.
R is preferably alkyl, aryl, hydroxy, or halogen, Y, Y and Y are preferably hydrogen or alkyl. R, Y, Y and Y are preferably of zero to about ten carbon atoms.
A is preferably phenyl, and insaid case, d is from zero to four.
When R, Y, Yl or Y are halo, they may be chlorine, fluorine, bromine or iodine.
The unsaturated compounds that may be used as starting materials in the preparation of the compounds of the present invention are of the following formula:
o-o= (oY,).
)l-I wherein subscript e and Z, Y, Y and Y are as hereinbefore described. As indicated by the broken line, the unsaturation is at bond 1 and 2 when e is equal to zero and at bond 2 and 3 when e is equal to one. These compositions include compounds such as benzoquinone, maleic anhydride, itaconic anhydride, malimide and maleic thioanhydride.
The starting mercaptophenol compounds of the present invention are of the formula: HS-A(R) OH; where in A, R and d are as hereinbefore described. Said compounds may be prepared by methods known in the prior art or by the procedure described in copending appllcation Ser. No. 597,228, filed Nov. 28, 1966, now abandoned and refiled as Ser. No. 666,915, filed Sept. 11, 1967, now U.S. 3,468,961. Mercaptophenols, such as o-mercaptophenol, p-mercaptophenol, 3,5-dimethyl Z-mercaptophenol, 4- phenyl-Z-mercaptophenol, 3-cyano-2-rnercaptophenol and 4-carboxy-3-mercaptophenol, are typical starting compounds.
The following reaction illustrates the process for the preparation of the novel compounds of the present mvention.
Subscripts d and e, and Z, A, R, Y, Y and Y are as hereinbefore described.
Although the reaction may be conducted in the absence of a solvent, it is normally conducted in the presence of a solvent. Typical solvents include benzene, toluene, xylene, heptane, hexane, chloroform, carbon tetrachloride, chlorobenzene, dioxane, N,N-dimethylforr nam1de, N-methyl-Z-pyrrolidone, tetrahydrofuran and dimethylsulfoxide.
Although the reaction may be conducted at a temperature of about zero to about 200 degrees centigrade, the preferred temperature is from about to about 150 degrees centigrade.
Although the reaction may be conducted in the absence of a catalyst, the time and temperature required to complete the reaction may generally be reduced by using a basic catalyst. A catalytic amount of about .05 mole of catalyst per mole of mercaptophenol is preferably employed. Suitable catalysts include salts of strong bases and alcohols or weak acids, amines, quaternary amine bases and alkali or alkaline earth metals or hydroxides. Examples of catalysts are sodium methylate, sodium acetate, potassium carbonate, triethyl amine, piperidine, triethylene diamine, trimethylbenzylammonium hydroxide and sodium or magnesium and sodium hydroxide.
The hydroxyarylthio succinic anhydrides and thioanhydrides of the present invention can be reacted with glycols or thioglycols to give the novel polyesters of the present invention.
4 Said novel polyesters contain at least ne unit of the formula Y, Y Y A, R and subscripts d and e fore described.
The preferred polyesters of the present invention are of the formula are as hereinbe- R and subscript d are as hereinbefore described. Typical glycols or thioglycols that may be used as starting compounds in the preparation of the polyesters of the present invention are as follows: diethylene glycol, ethylene glycol, a,w-dihydroxy[poly(ethyleneoxides)], l, 2-propylene glycol, 3,4-pentanediol, 1,10-decanediol, neopentyldiol, 1,4-cyclohexanediol, diethanol sulfide, 1,4-diethanolbenzene, 1,4-xylylenol, 1,4,5,6,7,7-hexachloro-2,3- bis(hydroxymethyl)bicyclo-(2.2.1 )-heptene-5, ethylenedithiol, hexamethylenedithiol, a,w-dimercapto(po1y(ethylenc sulfide) 1,4-bis(mercaptomethyl)cyclohexane, 1,12- dodecanedithiol and his (mercaptoethyhsulfide. Also, glycols and dithiols prepared by the oxyalkylation or thioalkylation of the above compounds and compounds such as 4,4'-isopropylidene diphenol, resorcinol, thiobisphenol, 4,4-dihydroxydiphenyl, aniline and methylamine.
In the process for the preparation of the novel hydroxyarylthio polyesters of the present invention, the glycol or thioglycol is reacted with the hydroxyarylthio succinic anhydride, or the corresponding dialkyl succinate, when a transesterification procedure is used, at atemperature of about 75 to about 250 degrees centigrade,for a period of about 3 to about 50 hours. No catalyst is required when the polyesterification is conducted by reaction of the hydroxyarylthiosuccinic anhydride. When a transesterification procedure is used useful catalysts are paratoluenesulfonic acid, or weakly acidic or basic catalysts such as calcium acetate or antimony triox ide. f
Standard polyesterification procedures are applicable. For example, the rate of esterification can be increased by hastening the elimination of the condensation products, ,water or alcohol. Typically this is accomplished by passing an inert gas stream through the reaction mixture or by maintaining the mixture under reduced pressure, Water can also be removed as it forms by conducting the esterifi-' cation in a water-imiscible solvent, such as toluene, whereby the water is distilled off asa component of an azeotropic distillate. The reaction is followed by periodically determining the carboxylic acid concentration or by monitoring the water or alcohol produced during the'course of the reaction.
The c'arboxylic reagent need not be a single compound, but can be composed of several carboxylic compounds, of which one, several, or all can be hydroxyarylthio-sub stituted. Also the second reactant can be a mixture of several glycols or dimercaptans, Typical non-phenolic carboxylic reagents are fumaric acid, maleic anhydride, phthalic anhydride, pyromellitic anhydride, diethyl fumarate, dimethyl terephthalate, dimethyl 1,4,5 ,6,7,7-hexachlorobicyclo-(2.2.1 -5 -heptane-2,3-dicarboxyl ate.
A portion of the glycol or thioglycol can be replaced by trior higher substituted polyols or polythiols to give across-linked 'polymen-Typical polyols are 1,1,1-trimethylolpropane, glycerol, pentaerythritol, and oxyalkylated derivatives derived from sorbitol, sucrose and phenylenediamine.
A portion of the carboxylic reagent can be replaced with unsaturated anhydride or ester, such as those mentioned above, for example, maleic anhydride. The resulting polyester can be crosslinked via these unsaturated bonds with a vinyl monomer such as styrene.
The phenolic polyester compositions of this invention can be converted to epoxy derivatives by reaction with, for example, epichlorohydrin.
. The phenolic polyester compositions of this invention can be converted to a polyester substituted with aliphatic hydroxyl groups by treatment with an alkylene oxide, (oxyalkylation), such as ethylene oxide or propylene oxide. These ester polyols are useful as reagents for preparing polyurethane polymers by reaction with diisocyanates or polyisocyanates. Typical isocyanates are toluene diisocyanates and the phosgenated reaction products of formaldehyde and aniline.
The hydroxyarylthiosuccinic anhydrides, succinimides and succinicthioanhydrides of the present invention are useful when incorporated chemically into condensation polymers as stabilizers or as providers of hydroxy groups. The hydroxyl groups are used to chemically attach polymer modifiers, such as dyes, antistatic agents, hydrophobic or .hydrophilic groups, and the like.
.positionsof the present invention with carbonyl compounds, e.g., formaldehyde or aetone, under acid conditions with or without additional phenol present, gives carboxylic substituted bisphenol or novolak materials which may be esterified with long-chain alcohols to give reagents useful for imparting chemically-bound plasticization to polymers, or which may be incorporated into polycarbonates, for example, to serve as cross-linking sites. Furthermore, reaction of the compounds of the present invention with carbonyl compounds under alkaline conditions gives methylol or resole type materials that will cure on heating.
The following examples will further illustrate specific embodiments of this invention. It should be understood however that these examples are given by way of illustration and not limitation. All temperatures are in degrees centigrade and all parts are by weight, unless otherwise indicated.
EXAMPLE 1 To a stirred solution of 980 parts of maleic anhydride (10.1 moles), 1 part of triethylenediamine and 5600 parts toluene, was added 1260 parts of a-mercaptophenol (10.0 moles) over about a 15 'minute period. The reaction was exothermic. After about one-half hour the reaction mixture was cooled to five degrees centigrade. From a resulting thick slurry, 1900 parts of product were obtained on filtration. Concentration of the filtrate and further filtration resulted in more product. The combined product was recrystallized from toluene in fractions. The first crop,
about 2040 parts, represented a 91 percent yield and "6 melted in the range of -130 degrees centrigrade. The total weight of all crystallization fractions corresponded to a yield of 98.5 percent. Theproduct was identified as 1-(2-hydroxyphenylthio) succinic anhydride.
Analysis- Calculated for C H S: Percent Phenolic hydroxyl 4. 4.47 Acid and anhydride 8.90 Anhydride 8.90 Found: i
Phenolic hydroxyl 4.40 Acid and anhydride 8.80 Anhydride 8.74
EXAMPLE 2 In a manner similar to Example 1, 5 parts of benzoquinone were reacted with 11.6 parts of o-mercaptophenol. About 7.4 parts of product were obtained. The product, having a melting point of 121-122 degrees centigrade, was identified as 5-(2-hydroxyphenylthio)-2-cyclohexen- 1,4-dione.
Analysz's Calculated for G i-1 0 8: C, 61.52 percent; H, 4.30
percent; S, 13.69 percent; OH, 7.24 percent. Found: C, 61.43 percent; H. 4.34 percent; S, 13.4
percent; OH, 7.38 percent.
EXAMPLE 3 In a manner similar to Example 1, 2,4-di-t'butyl-6-mer captophenol was reacted with maleic anhydride. The product, having a melting point of 137-139 degrees centigrade, was identified as 1-(2-hydroxy-3,5-di-t-butylphenylthio) succinic anhydride.
Analysis- Calculated for C H O S: C, 53.56 percent; H, 3.60
percent; S, 14.30 percent; OH, 7.57 percent. Found: C, 53.55 percent; H, 3.44 percent; S, 14.2
percent; OH, 7.45 percent.
EXAMPLE 4 To a solution of about 25 parts of tetrahydrofuran and 9.7 parts of maleimide, were added 12.6 parts of o-mercaptophenol during a 12 minute period. The reaction mixture was maintained below about 50 degrees centigrade during the addtion by means of an ice bath. After the reaction mixture had stood for several days, the tetrahydrofuran was stripped under reduced pressure. The residue was crystallized from benzene to give 14.7 parts of product. The product, identified as (Z-hydroxyphenylthio) succinimide, had a melting point of 1120-1145 degrees centigrade.
Analysis- Calculated for C H O NS: S, 14.3 percent; OH,
4.48 percent. Found: S, 14.02 percent; OH, 4.4 percent.
In a similar manner and in separate experiments, ethylmaleic thioanhydride and 1-ethyl-2-methylenemaleic anhydride are reacted with 3,5-dimethyl-Z-mercaptophenol to yield the following respective products: 1-ethyl-2-(2-hydroxy-4,6-dimethylphenylthio) succinic thioanhydride and 1 ethyl-2-(2-hydroxy-4,6-dimethylphenylthiomethylene) succinic anhydride.
EXAMPLE 5 To 58.3 parts of diethylene glycol were added 112 parts (0.5 moles) of (Z-hydroxyphenylthio) succinic anhydride. The mixture was warmed to a temperature of 85 degrees centigrade at which temperature the anhydride went into solution. The solution was heated to 180 degrees centigrade for 75 minutes during which period 6 parts of water were distilled oif. The system was put under millimeters of reduced pressure and the heating con- .tinued. for *one hour at 190 degrees-centigrade and for three hours at 170 degrees centigrade. The resulting product was'a golden yellow resin.
Analysis- In a similar" manner, (2-hydroxyphenylthio)succinic anhydride is reacted with ethylenedithiol to form a poly ester.
EXAMPLE 6 A low molecular weight resole was prepared by a phenol, formaldehyde and sodium hydroxide condensation reaction. Equal amounts of said resole and the polyester of Example were stored at 85 to 95 degrees centigrade for three days. The product was a golden yellow hard resin. When the resole is subjected to the same conditions, it becomes a deep red resin.
EXAMPLE 7 Analysis Milliequivalents per gram Calculated hydroxy value 3.75 Foundhydroxy value 3.81
Molecular weight: 847
While there have been described various embodiments of the present invention, the methods and compositions described are not intended to be understood as limiting the scope of the invention as it is realized that changes therein are possible.
What is claimed is:
1. A polyester comprising at least one unit of the formula wherein (a) e is from zero to one and d is from zero to about six;
' (b) provided that:
(1) when 2 is zero, Y is hydrogen; and (2) when e is one, Y is hydrogen;
(c) Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano andhalogen;
. (d) w is selected from the group consisting of O- and (e) A is aryl of six to 18 carbon atoms; and
(f) R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cy no, carboxy and halogen.
2. A process for-premring the; polyester of Claim 1, comprising reacting a compound of the formula M I wherein: g g .1
(a) e is from zero to one and d is from zero to'abou't Six; G
'(b) provided that:
( 1) when e is zero, Y is hydrogen; and (2) when e is one, Y is hydrogen;
(c) Y, Y and Y are of zero to about 2O carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
(d) Z is selected from the group consisting of --O and (e) A is aryl of six to 18 carbon atoms; and
(f) R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halo I V with a glycol or thioglycol at a temperature of about 75 degrees centigrade to about 250 degrees centigrade.
3. A polyester according to the processof Claimv 2 of the formula:
wherein R is selected from the group consisting of alkyl, aryl, hydroxy and halogen and d is from zero to six.
5. The polyester of Claim 4 wherein d is 0.
6. A polyester of Claim 1 wherein:
(a) e is from zero to one and d is from zero" to about SIX;
(b) provided that:
( 1) When e is zero, Y is hydrogen; mm (2) when e is one, Y is hydrogen;
(c) Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;
(d) w is 0;
(e) A is aryl of six to 18 carbon atoms; and
(f) R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, carboxy and halogen.
9 10 7. A process for preparing the polyester of Claim 6, (d) Zis O; comprising reacting a compound of the formula (e) A is aryl of six to 18' carbon atoms; and
O (f) R is of zero to about 20 carbon atoms and is selected II I from the group consisting of alkyl, aryl, alkaryl,
5 aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy,
l mercapto, carboxy and halo with a glycol or thio-glycol.
c CY esA R II 2) )d References Cited Y UNITED STATES PATENTS wherein: 10 (a) e is from zero to one and d is from zero to a out 3 210,37 19 5 smith 2 3 5 3,472,879 10/1969 Isard et a1 260-346.2 provlded thatI 3,664,986 5/1972 MacDonald 260-78 R (1) when e zero, Y is hydrogen; and (2) w 8 is Y2 is y g 15 LESTER L. LEE, Primary Examiner (c) Y, Y and Y are of zero to about carbon atoms and are independently selected from the group con- US. Cl. X.R.
sisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano 260-47 R, 50, 53 R, NK, 470 and halogen;
UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION I Patent No. 3 Dated August 7 97'+ fl Emi l J. Geering and Norman W. Dachs It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
l" Column 1 line 53 "Oragnic" should read --0rganic--. Column 3, lines 70-71 "magnesium and" should read --'-magnesium metal and--. I Column 9, line 7, that part of the Formula reading -S--A-(R) should read -S-A-(R) Signed and sealed this 21st day of January 1975.
(SEAL) Attest:
MCCOY n. GIBSON JR. c. MARSHALL DANN Attesting Off cer Commissioner of Patents
US00115778A 1968-08-05 1971-02-16 Polyesters prepared from hydroxyarylthio anhydrides Expired - Lifetime US3832329A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113318A1 (en) * 1982-12-29 1984-07-11 Ciba-Geigy Ag (4-Hydroxyphenylthio)-imide stabilizers
US4559379A (en) * 1983-09-14 1985-12-17 Ciba Geigy Corporation 4-Hydroxyphenylthio substituted stabilizers for polymers
US20060122075A1 (en) * 2004-12-06 2006-06-08 Anderson Linda K Non-gelled curable compositions containing imide functional compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113318A1 (en) * 1982-12-29 1984-07-11 Ciba-Geigy Ag (4-Hydroxyphenylthio)-imide stabilizers
US4559379A (en) * 1983-09-14 1985-12-17 Ciba Geigy Corporation 4-Hydroxyphenylthio substituted stabilizers for polymers
US20060122075A1 (en) * 2004-12-06 2006-06-08 Anderson Linda K Non-gelled curable compositions containing imide functional compounds
US7705110B2 (en) * 2004-12-06 2010-04-27 Ppg Industries Ohio, Inc. Non-gelled curable compositions containing imide functional compounds

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